柠檬酸三钠对Co2+-Ni2+-Fe3+-CO32- LDHs形貌及其离子交换性能的影响

doi:10.15541/jim20140099

摘要/Abstract

摘要：

Co²⁺/Ni²⁺/Fe³⁺摩尔比为0.5/3/1, 采用络合剂柠檬酸三钠协助均相沉淀技术, 制备了Co²⁺-Ni²⁺-Fe³⁺-LDHs层状材料, 研究了柠檬酸三钠用量对Co²⁺-Ni²⁺-Fe³⁺ LDHs层间距及形貌的影响。在此基础上, 研究了不同层间距和不同形貌Co²⁺-Ni²⁺-Fe³⁺--LDHs层状材料的离子交换性能, 即Co²⁺-Ni²⁺-Fe³⁺-LDHs层状材料在NaCl-HCl的离子交换体系中进行阴离子交换反应, 生成Co²⁺-Ni²⁺-Fe³⁺-Cl^--LDHs层状材料。研究结果表明: 当柠檬酸三钠用量为0.6~1.0 mmol/L时, 所制备的LDHs层间距为0.776 nm, 片层结构分散性较好, 产物的较大层间距和较好形貌使其仍保持良好的离子交换性能, 并通过离子交换反应可分别得到、、、及CH₃(CH₂)₁₁插层Co²⁺-Ni²⁺-Fe³⁺-LDHs层状衍生材料; 当柠檬酸三钠用量在1.5 mmol/L时, 所制备的LDHs层间距为0.770 nm和0.691 nm, 片层结构团聚并成玫瑰花形貌, 使得客体离子较难插入到层间, 产物的离子交换性能降低; 当柠檬酸三钠的量增加到3.0 mmol/L时, 得到的LDHs层间距为0.681 nm, 片层结构变小, 团聚现象加剧, LDHs片完全交错生长成球状形貌, 产物完全失去了离子交换性能。

关键词: Co2+-Ni2+-Fe3+ LDHs, 柠檬酸三钠, 离子交换反应, 形貌

Abstract:

Co²⁺-Ni²⁺-Fe³⁺--LDHs (layered double hydroxides, LDHs) materials were synthesized by using trisodium citrate (TSC) assisted homogeneous precipitation technology. The influences of TSC amount on the basal spacing and morphology of the obtained materials were investigated by changing TSC amount from 0.6 mmol/L to 3.0 mmol/L. Then the deintercalation of carbonate ions from a Co²⁺-Ni²⁺-Fe³⁺--LDHs materials with different basal spacing and shape morphology were investigated by socking in a NaCl-HCl mixed solution. The results indicated that LDHs with basal spacing of 0.776 nm and well-defined hexagonal shapes was obtained when TSC optimized amount was between 0.6-1.0 mmol/L, exhibiting a good anion exchange property. Thus a series of materials intercalated by, , , and CH₃(CH₂)₁₁anions were obtained. When TSC amount was up to 1.5 mmol/L, a new layered structure of LDHs with basal spacings of 0.770 nm and 0.691 nm was observed with rose-like morphology consisting of reunion hexagonal shapes, decreasing its anion exchange property. When TSC amount was further increased to 3.0 mmol/L, the layered structure of LDHs with a basal spacing of 0.681 nm was observed with ball-shaped like morphology consisting of reunion hexagonal shapes, leading to its anion exchange property disappear.

Key words: Co2+-Ni2+-Fe3+ LDHs, trisodium citrate, ion exchange reaction, morphology

中图分类号:

O611
O614

马向荣, 刘宗怀. 柠檬酸三钠对Co²⁺-Ni²⁺-Fe³⁺-CO₃^2- LDHs形貌及其离子交换性能的影响[J]. 无机材料学报, 2014, 29(12): 1306-1312.

MA Xiang-Rong, LIU Zong-Huai. Effect of Sodium Citrate Amount on Morphology and Anion Exchange Property of Co²⁺-Ni²⁺-Fe³⁺-CO₃^2- LDHs[J]. Journal of Inorganic Materials, 2014, 29(12): 1306-1312.

图/表 7

图 1 不同TSC用量制备的LDHs产物的XRD 图谱

Fig. 1 XRD patterns of the products prepared with various TSC amounts (a) S1-LDHs; (b) S2-LDHs; (c) S3-LDHs; (d) S4-LDHs

表 1 不同TSC浓度下所得产物Co/Ni/ Fe的摩尔比及用HCl-NaCl处理后的产物 C、Cl元素含量分析结果

Table 1 Co2+/Ni2+/ Fe3 molar ratios in samples prepared with different TSC amounts and analysis on C and Cl elements in samples treated with a NaCl-HCl mixed solution

TSC amounts/(mmol·L^-1)	Samples	Co²⁺/Ni²⁺/Fe³⁺ molar ratio	C/wt%	Samples	C/wt%	Cl/wt%
0.5	S1-LDHs	1.00/6.01/2.01	1.169	D1-LDHs	0.001	6.841
1.0	S2-LDHs	1.00/5.85/2.00	1.188	D2-LDHs	0.002	6.953
1.5	S3-LDHs	1.00/5.53/1.98	1.217	D3-LDHs	0.727	2.868
3.0	S4-LDHs	1.00/5.04/2.03	1.392	D4-LDHs	1.345	0.274

图 2 LDHs层间脱除过程示意图

Fig. 2 A model for the deintercalation of from a LDHs

图 3 不同TSC用量制备的LDHs产物及其经HCl-NaCl溶液处理后产物的XRD 图谱

Fig. 3 XRD patterns of the products prepared with various TSC amounts and their corresponding products by treatment with a mixture solution of HCl-NaCl (a) S1-LDHs; (a°) D1-LDHs; (b) S2-LDHs; (b°) D2-LDHs; (c) S3-LDHs; (c°) D3-LDHs; (d) S4-LDHs; (d°) D4-LDHs

图 4 不同TSC用量制备的LDHs产物及其用HCl-NaCl处理以后所得产物的FT-IR图谱

Fig. 4 FT-IR spectra of the obtained products in various TSC amounts and their corresponding products after treatment with a mixture of HCl-NaCl (a) S1-LDHs; (a°) D1-LDHs; (b) S2-LDHs; (b°) D2-LDHs; (c) S3- LDHs; (c°) D3-LDHs; (d) S4-LDHs; (d°) D4-LDHs

图 5 不同TSC用量制备的LDHs产物的SEM照片

Fig. 5 SEM images of the products prepared at various TSC amounts (a) S1-LDHs; (b) S2-LDHs; (c) S3-LDHs; (d) S4-LDHs

图 6 不同阴离子插层的产物Co2+-Ni2+-Fe3+-LDHs的FT-IR图谱(A)和XRD图谱(B)

Fig. 6 FT-IR spectra (A) and XRD patterns (B) of Co2+- Ni2+-Fe3+-LDHs incorporated by different anions

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柠檬酸三钠对Co²⁺-Ni²⁺-Fe³⁺-CO₃^2- LDHs形貌及其离子交换性能的影响

Effect of Sodium Citrate Amount on Morphology and Anion Exchange Property of Co²⁺-Ni²⁺-Fe³⁺-CO₃^2- LDHs

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